US20120064406A1 - Electrode material, method for producing same, and lithium ion secondary battery - Google Patents

Electrode material, method for producing same, and lithium ion secondary battery Download PDF

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US20120064406A1
US20120064406A1 US13/009,921 US992107A US2012064406A1 US 20120064406 A1 US20120064406 A1 US 20120064406A1 US 992107 A US992107 A US 992107A US 2012064406 A1 US2012064406 A1 US 2012064406A1
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metal
active substance
electrode material
source compound
battery
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US20110176235A1 (en
US9156404B2 (en
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Hiroshi Sato
Takayuki Fujita
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Namics Corp
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Namics Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an electrode material and a method for producing the same, and particularly, an electrode material preferably used in a lithium ion secondary battery and a method for producing the same.
  • a nonaqueous lithium ion secondary battery has characteristics of high energy density, from which a high voltage exceeding the electrolysis voltage of water can be obtained. Due to having such characteristics, utilization of a lithium ion secondary battery in a hybrid car has been studied.
  • a lithium ion secondary battery conventionally contains an active substance with low conductivity, which constitutes an electrode, and thus has a defect of high internal resistance.
  • a method for mixing an auxiliary conductive material such as carbon in an active substance is disclosed (Patent Document 1).
  • Patent Document 2 discloses a technique of securing conductivity of an active substance by coating metal material particles with a particle size of 0.005 ⁇ m to 10 ⁇ m on the surface of the electrode active substance.
  • Patent Document 2 describes an example in which titanium and aluminum are used as metal material particles. These metal fine particles have extremely high surface activity and there is a possibility of dust explosion by radical oxidation, thus being difficult in handling in the fine particle state.
  • “application” is exemplified for a method for coating metal material particles (paragraph [0024]), but there is no description about a specific method thereof. For example, Patent Document 2 does not describe how to handle metal fine particles having high activity safely without causing dust explosion.
  • Patent Document 2 discloses the invention sufficiently enough to be easily reproduced by a person skilled in the art.
  • the coating method described in Patent Document 2 is adhering metal particles on an active substance by a physical method which is not accompanied by a chemical reaction. Therefore, surfaces of these metal fine particles are generally formed from layers of thin oxide films.
  • An oxide film of titanium or aluminum, which is a metal particle exemplified in Patent Document 2 is hard to be a metal by reduction using chemical agents or gas such as hydrogen due to the properties of the elements, and is generally a semiconductor or an insulator. Accordingly, even if metal particles are coated on an active substance in the method of Patent Document 2, in actuality, it is difficult to obtain conductivity similar to metals.
  • Patent Document 2 describes that a method such as atmospheric plasma can also be used as a method for coating metal material particles (paragraph [0009]).
  • a method such as atmospheric plasma can also be used as a method for coating metal material particles (paragraph [0009]).
  • CVD and PVD are described as conventional methods with defects, the method such as atmospheric plasma is hardly considered to be plasma CVD and thus unclear with respect to how to specifically use plasma.
  • An object of the present invention is to provide a method for producing an electrode material having high conductivity safely, and the electrode material having high conductivity, mainly in order to reduce internal resistance of a lithium ion secondary battery and improve input/output characteristics.
  • the present invention (1) is an electrode material for a lithium ion secondary battery obtained by depositing a metal generated from a metal source compound by thermal decomposition and/or reduction on an active substance.
  • the present invention (2) is the electrode material according to the invention (1), wherein the metal deposits on the active substance in a state that the active substance and the metal are in contact without interposition of an oxide therebetween.
  • the present invention (3) is the electrode material according to the invention (1) or (2), wherein the metal source compound is any one of an organic metal compound, an organic metal complex, a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide, or a substance obtained by combining the compounds.
  • the metal source compound is any one of an organic metal compound, an organic metal complex, a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide, or a substance obtained by combining the compounds.
  • the present invention (4) is the electrode material according to one of the inventions (1) to (3), wherein the metal is any one of nickel, copper, platinum, paradigm, silver, zinc, cobalt, vanadium, tungsten, molybdenum, chromium, and iron, or a mixed material or a metal alloy thereof.
  • the present invention (5) is an active substance paste for a battery formed by mixing and dispersing at least an electrode material according to one of the inventions (1) to (4) and a vehicle.
  • the present invention (6) is a wet type or all solid-state lithium ion secondary battery formed using the active substance paste for a battery according to the invention (5).
  • the present invention (7) is a method for producing an electrode material, including at least a step of producing primary powder by mixing and dispersing an active substance and a metal source compound, and a step of producing an electrode material by generating a metal from the metal source compound by thermal decomposition of the primary powder and depositing the metal on the active substance.
  • the present invention (8) is a method for producing an electrode material, including at least a step of producing primary powder by mixing and dispersing at least an active substance and a metal source compound, and a step of producing an electrode material by generating a metal from the metal source compound by vapor phase reduction of the primary powder and depositing the metal on the active substance.
  • the present invention (9) is a method for producing an electrode material, including at least a step of producing primary powder by mixing and dispersing an active substance and a metal source compound, a step of producing secondary powder by thermal decomposition of the primary powder, and a step of producing an electrode material by generating a metal from the metal source compound by vapor phase reduction of the secondary particles and depositing the metal on the active substance.
  • the present invention (10) is the method for producing an electrode material according to one of the inventions (7) to (9), wherein the metal source compound is anyone of an organic metal compound, an organic metal complex, a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide, or a substance obtained by combining the compounds.
  • the metal source compound is anyone of an organic metal compound, an organic metal complex, a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide, or a substance obtained by combining the compounds.
  • the present invention (11) is the method for producing an electrode material according to one of the inventions (7) to (10), wherein the metal comprises any one of nickel, copper, platinum, paradigm, silver, zinc, cobalt, vanadium, tungsten, molybdenum, chromium, and iron, or a mixed material or a metal alloy thereof.
  • FIG. 1 is a cross-sectional view of the order of steps to describe a preferable embodiment of the method for depositing metal particles of the present invention.
  • FIG. 2 is XRD measurement data of a sample obtained by depositing nickel particles on an active substance.
  • FIG. 3 is XRD measurement data of a sample obtained by depositing copper particles on an active substance.
  • FIG. 4 is a pattern cross-sectional view of an active substance having conventional metal material particles.
  • the inventors of the present application investigated a cause of not obtaining a remarkable effect on improvement in conductivity even when metal particles are coated on the surface of an active substance in the method described in Patent Document 2. As a result, they found that the reason is because when metal particles are coated in a physical method, for example, a metal oxide is formed in a reaction with oxygen in the atmosphere, and thus, the active substance and the metal particles are in contact with interposition of the metal oxide having low conductivity.
  • an electrode material having high conductivity can be produced without forming an oxide.
  • the method for producing an electrode material of the present invention is a useful production method having excellent characteristics in terms of the following items (2) to (5).
  • any one of an organic metal compound, an organic metal complex, a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide, or a substance obtained by combining the compounds is preferably used as the above described metal source compound.
  • any of thermal decomposition, vapor phase reduction, and liquid phase reduction, or a method combining the above methods is preferably used.
  • the inventors of the present application found that use of these materials and treating in these methods enable effective deposition of metal particles on the surface of an active substance, which, as a result, makes it possible to smooth provision of electrons to the active substance and discharge of electrons from the active substance, and input/output characteristics of a lithium ion secondary battery constituted with the active substance thus obtained can be improved, and they achieved completion of the present invention.
  • the active substance and the auxiliary conductive powder can secure conductivity only by point contact; on the contrary, according to the present invention, deposition of metal particles on the surface of an active substance is performed by a chemical deposition method; therefore, contact areas of the active substance and the metal particles increase and higher conductivity can be thus realized.
  • FIG. 1 is a cross-sectional view of the order of steps to describe a preferable embodiment of the method for depositing metal particles of the present invention.
  • metal elements having higher electron conductivity are preferably used as compared to electron conductivity of carbon particles.
  • organic metal compounds are preferably used.
  • examples include organic acid metal compounds such as silver acetate, copper acetate, copper formate, nickel acetate, copper acetate, zinc acetate, zinc formate, cobalt acetate and iron acetate; an ethylenediaminetetraacetic acid (EDTA) metal complex, an acetyl acetonate complex, and metal soaps.
  • EDTA ethylenediaminetetraacetic acid
  • a metal compound containing a carbonate radical, a metal hydroxide, and a metal hydroxide peroxide can also be used instead of organic metal compounds.
  • examples include silver carbonate, basic nickel carbonate, and basic copper carbonate.
  • Metal carbonate and organic metal complexes, and basic metal compounds generate gas in thermal decomposition and reduction and the gas does not have toxicity such as water, oxygen and carbon dioxide gas, and the metal carbonate and organic metal complexes, and basic metal compounds are preferable from the viewpoint of safety of handling operation for carrying out the present invention.
  • the above described metal source compounds can be used by mixing with one or more metal compounds.
  • an active substance, and nickel acetate and copper acetate are appropriately mixed and dispersed and the resultant is thermally decomposed in a reduction atmosphere and an inert gas atmosphere, the metals of nickel and copper can be simultaneously deposited on the surface of the active substance, and an alloy can also be formed.
  • Controlling ratios in use of plural kinds of metals to be deposited and a thermal decomposition temperature enables battery design with flexibility in crystal diameters and particle diameters of the metal species to be deposited, electrical conductivity, and battery characteristics.
  • metals to be deposited one of nickel, copper, platinum, paradigm, silver, zinc, cobalt, vanadium, tungsten, molybdenum, chromium, and iron, or a mixed material or a metal alloy thereof is preferably used.
  • an organic metal compound that is to be the metal source a substance with a small molecular weight is preferably used.
  • the order of more preferable organic metal compounds is metal formate>metal acetate>metal oxalate>metal soaps.
  • Materials of an active substance which can be preferably used for the electrode material of the present invention, are not limited to specific substances, and any substance can be preferably used as long as the materials are substances having discharge and storage ability of a lithium ion.
  • a substance having an electric potential occurring discharge and storage of a lithium ion in the noble side is the positive electrode
  • a substance having an electric potential occurring discharge and storage of a lithium ion in the base side is the negative electrode.
  • examples of the lithium ion donor include complex oxides, complex sulfates, complex nitrides, and fluoride oxides, which are constituted with lithium and one or more metals.
  • examples of the lithium ion acceptor include metal oxides, metal sulfates, and metal nitride, which are constituted with one or more metals, complex oxides, complex nitrides, and complex sulfates, which are constituted with lithium and one or more metals, phosphorus sulfide compounds, carbon, and metal alloys.
  • examples include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiCuO 2 , LiCoVO 3 , LiMnCoO 4 , LiMnCrO 4 , LiCoPO 4 , Li 2 CoPO 4 F, Li 2 CoSiO 4 , LiFePO 4 , Li 4/3 Ti 5/3 O 4 , LiTiO 2 , LiM1 s M2 t O u (M1 and M2 are transfer metals, and s, t and u are arbitrary positive numbers), MoS 2 , TiS 2 , MnO 2 , NiPS 3 , a lithium-aluminum alloy, high graphitized soft carbon, low graphitized soft carbon, low-temperature calcinated carbon, and hard carbon.
  • an active substance is LiMn 2 O 4
  • the structure of the active substance is easily changed as described above. Therefore, a metal source compound having a small molecular weight, for example, formic acid metal, is used, and a low-temperature heat treatment is preferably performed in an inert gas atmosphere.
  • LiCoO 2 When an active substance is LiCoO 2 , Cu can be used as the metal species of a metal source compound. Since LiCoO 2 and Cu are hardly reacted, even when, for example, LiCoO 2 and copper formate are mixed and the mixture is subjected to thermal decomposition, copper oxide and metal copper generated by the decomposition hardly cause an unnecessary reaction with LiCoO 2 .
  • Ni can also be used as the metal species. Since LiNiO 2 is a positive electrode active substance, in the case of synthesis of a positive electrode material, for example, even when LiCoO 2 and nickel formate are combined to be treated, LiCo (1-x) Ni x O 2 that is possibly generated is also a positive electrode active substance, and thus, there is no fear to degrade characteristics of a battery.
  • Li 4 Ti 5 O 12 that is not easily changed in the structure even with a heat treatment in a reduction gas atmosphere can select a broad range of substances as a metal source compound.
  • examples such as Ni, Cu, and Co can be selected.
  • the electrode material according to the present invention is made of an active substance on which metal particles are deposited on the surface thereof.
  • Such an electrode material is generally made of an active substance and a metal source compound, which are processed into a powdered state as raw materials, and firstly, these raw materials are uniformly dispersed to be mixed in either method for dry mixing and dispersion or wet mixing and dispersion.
  • Initial raw materials are not necessarily processed into a powdered state, but may be in a balky state, or an aggregated state. Even in such cases, the raw materials are crushed in the mixing and dispersion step to be processed into a powdered state.
  • the dry mixing and dispersion is a method for mixing and dispersing without using a liquid, and for example, the raw materials can be processed using devices such as a vibration mill, a planetary boll mill, and a pot mill.
  • the wet mixing and dispersion is a method for mixing and dispersing in which powder that is a raw material is mixed with a liquid to form a slurry and processed and, for example, the slurry can be processed using a device such as a bead mill.
  • a bead mill is a device filled with crushing media called beads in a rotation container called a crushing room.
  • the slurry is sent into the crushing room with a pump and beads are collided with the slurry to thus finely crush and disperse raw materials. Finally, the slurry and the beads are separated by a centrifugal device and a screen which are located at the outlet of the crushing room.
  • an appropriate method may be used according to kinds of raw materials to be used.
  • a method other than the dry mixing and dispersing and the wet mixing and dispersing can be used.
  • the concentration range of the metal source compound preferably appropriately set within an optimal range according to a purpose of use of a battery, an active substance material, and a metal source compound material.
  • secondary batteries used for a calculator and an alarm display light on a road, which are equipped with solar batteries have approximately constant power consumption and priority of high output characteristics is low.
  • a battery is designed to increase an amount of an active substance.
  • output characteristics are emphasized in a secondary battery for a hybrid car, and thus, a battery is designed to have a higher concentration of a metal source compound.
  • a minimum concentration of a deposition metal is set so that electrical resistance between the active substance in the electrode and the collector electrode can be effectively reduced, and a maximum concentration of the deposition metal is set to the level of not inhibiting transfer of a lithium ion between the active substance in the electrode and an electrolyte layer, and a concentration of a metal source compound is preferably set within the ranges.
  • the concentration of the metal source compound is preferably set to 30 to 70 vol % in the range that particles can retain continuity in three dimensions in consideration of the percolation theory.
  • powder obtained from an active substance and a metal source compound by dry mixing and dispersion are heated at a higher temperature than the thermal decomposition temperature of the metal source compound in the atmosphere as being the powder or after forming into a molded article, thereby depositing a metal or a metal oxide on the surface of the active substance. Reduction in a production cost is possible by treating in the atmosphere.
  • thermal decomposition may be performed in an inert gas atmosphere, or after performing thermal decomposition in the atmosphere, liquid phase reduction or vapor phase reduction may be carried out to reduce the metal oxide and deposit a metal. Additionally, thermal decomposition is not performed, and powder obtained in mixing and dispersion or a molded article formed from the powder may be directly subjected to liquid phase reduction or vapor phase reduction to deposit metal particles.
  • a slurry obtained by wet mixing and dispersion of an active substance and a metal source compound is dried to evaporate a solvent and the dried product is fractured and powdered, and then the powder is subjected to a heat treatment and a reduction treatment in the same manner as in the case of the above described dry mixing and dispersion to thus obtain deposition of metal particles.
  • Examples of an equipment used in drying the slurry include a slurry dryer, a spray dryer, a band dryer, and a batch dryer.
  • a metal source compound is desirably dried with keeping high dispersibility, and a spray dryer is preferably used.
  • the drying step may double with a thermal decomposition step, and by setting a drying temperature by the dryer as described above at a higher temperature than the thermal decomposition temperature of the metal source compound, deposition of metal particles can be obtained.
  • Vapor phase reduction can be carried out by a heat treatment in a reductive gas atmosphere such as hydrogen.
  • a heat treatment temperature and time may be suitably set depending on materials of an active substance and a metal source compound to be treated.
  • a fusing agent for the purpose of promoting flowability of the surface of an active substance in mixing and dispersing the active substance and a metal source compound by the above technique. Due to promotion of the surface flowability of the active substance in the thermal decomposition step, bond of the active substance and a deposited metal or a deposited metal oxide is more potent, and as a result, a contact area between these deposited products and the active substance increases and electron conductivity becomes preferable.
  • Determination of an appropriate temperature and heating conditions in the step of depositing a metal or a metal oxide from a mixture of an active substance and a metal source compound by thermal decomposition can be made by a measurement of a heat weight change (TG) of the metal source compound.
  • TG heat weight change
  • thermal decomposition is preferably performed at a temperature as low as possible.
  • the upper limit of the heating temperature can also be determined by a heat weight change, differential calories (TG-DTA) and a temperature increase X-ray diffraction structural analysis of the active substance in the same manner.
  • a temperature at which the active substance is not changed in its structure and lithium diffusion resistance in the active substance does not increase is to be the upper limit of the thermal decomposition.
  • a metal deposited active substance obtained in the present invention is mixed and dispersed with a suitable vehicle, dispersing agent, and the like, to form a paste, and an active substance paste for a lithium ion secondary battery can be prepared.
  • An auxiliary conductive material, a rheology modifier, and the like may be suitably further added according to battery performance to be required.
  • a method for producing a wet type lithium ion secondary battery will be described below.
  • the paste prepared in the above described method is applied on a collecting electrode foil to prepare an active substance coated foil.
  • Two kinds of active substance coated foils having different lithium ion discharge and storage electric potentials are prepared, a separator for securing electron insulation between these active substance coated foils, and an unwoven fabric for keeping a nonaqueous electrolyte solution on the surface of the active substance are arranged to constitute a lithium ion secondary battery.
  • a metallic foil such as an aluminum foil and a copper foil can be mainly used for the collecting electrode foil.
  • the collecting electrode foil is not limited to these materials, and any metallic foil can be used as long as it is a metallic foil that does not cause chemical change accompanying to a charge and discharge reaction of a battery.
  • any metallic foil can be used for the nonaqueous electrolyte solution and supporting electrolyte.
  • known ones can be used for them.
  • an ambient temperature molten salt (ionic liquid) may be suitably used.
  • a solid electrolyte slip made of fine powder having an atomic skeleton structure capable of diffusing a lithium ion, a binder, a dispersing agent, and a rheology modifier is formed into a thin film on a substrate by the doctor blade method and dried, then the paste prepared in the above described method is applied and printed, and further dried to thus obtain an active substance-coated-solid electrolyte sheet.
  • active substance-solid electrolyte sheets are prepared as described above, then laminated alternately and fired at once, thereafter electrically jointing the same active substances to thus constitute a lithium ion secondary battery.
  • metallic fine particles deposited on the surface of the active substance are molten so as to fill gaps of adjacent active substance particles, and the metallic fine particles are changed from a scattering particle state to a continuing matrix state. Accordingly, an ideal electron conductive path is formed in the active substance.
  • a paste to be applied on a solid electrolyte sheet may be applied in plural layers of several kinds of pastes having different ratios of the active substance and the deposited metal. Making layers having different ratios of the active substance and the deposited metal enables forming a more optimal metal matrix structure.
  • the all solid-state secondary battery is prepared by one-time firing, it is preferable to select a firing environment according to a metal species that is deposited on the surface of an active substance used in an active substance paste.
  • a metal species that is deposited on the surface of an active substance used in an active substance paste For example, when a metal that is easily oxidized by heating in the atmosphere is used, it is preferable to perform firing in a nitrogen atmosphere or in a reducing gas atmosphere in order to suppress oxidation in one-time firing.
  • Patent Document 2 discloses a technique of further forming a metallic coating film on a coating film of an active substance coated with metallic material particles on the surface thereof by performing electroless plating (paragraph [0012]) or chemical plating (paragraph [0026]). Electroless plating or chemical plating is one kind of liquid phase reduction in a broad sense.
  • Patent Document 2 describes that, in general, when the above described metallic coating film is directly formed on an active substance, it is necessary to etch the active substance before formation of the coating film, and, if the coating film is formed, the etching step is unnecessary (paragraph [0012]).
  • an etching treatment is unnecessary.
  • Patent Document 3 describes a nonaqueous secondary battery containing a complex made of silicon powder capable of inserting and discharging a lithium ion to a negative electrode material and a conductive metal imparting conductivity to silicon as a negative electrode active substance. It is described in Patent Document 3 that the conductive metal is obtained by reduction deposition of the conductive metal on silicon with an aqueous solvent (paragraph [0010]). However, an example of liquid phase reduction described in Patent Document 3, copper is deposited by reducing copper sulfate. However, from the viewpoints that, in treating steps, formaldehyde having toxicity is used, and vacuum dry is performed since copper is a substance that is easily oxidized, there are problems with respect to safety and a production cost. On the contrary, the present invention is an excellent technique with high safety and a low production cost as compared to Patent Document 3 in such points.
  • Patent Document 4 describes a technique of producing a negative electrode active substance made of metal element doped silicon oxide powder by heating silicon oxide and a metal to generate a mixed gas and depositing active substance powder on a cooling substrate.
  • a preferable heating temperature is set from 1100 to 1600° C.
  • the technique described in Patent Document 4 is vaporizing a metal to deposit the metal on an active substance, and the metal is not generated by chemical change such as reduction and decomposition, which is different from the present invention in this point.
  • the high-temperature heat treatment as described in Patent Document 4 can be applied to a substance such as silicon oxide, which hardly causes thermal decomposition even at a high temperature, but is difficult in applying to a substance with comparatively high volatile such as lithium that is exemplified as a preferable active substance in the present invention.
  • a heat treatment is performed at such a high temperature, there is fear to react an active substance and a metal, and also in this respect, the techniques described in the present invention and Patent Document 4 are different.
  • Patent Document 5 discloses a lithium ion secondary battery provided with an electrode material obtained by forming a transfer metal oxide coating film on a nickel mesh.
  • the nickel mesh functions as a conductive material
  • the transfer metal oxide coating film functions as an active substance.
  • Patent Document 5 describes that a transfer metal hydroxide is deposited on the mesh, and then thermally decomposed to form a transfer metal oxide coating film, or the mesh is immersed in an acetic acid metal solution, and then thermally decomposed to form a transfer metal oxide coating film.
  • the structure of the electrode material described in Patent Document 5 is different from the electrode material in the present invention in an arrangement of an active substance and a conductive substance.
  • the structure of the electrode material described in Patent Document 5 is a structure in which a metallic film is formed on a conductive material and thus does not function as an electrode material. Furthermore, the electrode material described in Patent Document 5 is a material with a brittle transfer metal oxide coating film and there is a problem that when the material is tried to be processed after deposition, the transfer metal oxide coating film is peeled off. Therefore, there is a problem that a produced electrode material cannot be formed into a powdered state or a paste state and processed into a molded article for a battery with a different shape and size as the electrode material of the present invention can.
  • thermal decomposition temperatures of metal source compounds and active substances in various environments were measured using TG-DTA.
  • Nickel acetate, copper acetate, zinc acetate, and silver acetate were used as the metal source compounds, and lithium manganate, lithium cobalt oxide, lithium cobalt phosphate, lithium cobalt silicate, and lithium titanate were used as the active substances. All measurements were performed at a temperature increase rate of 200° C./hr, and weight changes of the samples were measured to be used as a target for determining decomposition temperatures.
  • an experiment of confirming whether metal particles are deposited or not was carried out on these active substances using the deposition method according to the present invention.
  • Nickel acetate, copper acetate, zinc acetate, and silver acetate were used as the metal source compounds, and lithium manganate, lithium cobalt oxide, lithium cobalt phosphate, lithium cobalt silicate, and lithium titanate were used as the active substances.
  • the metal source compound and the active substance were mixed and dispersed in a dry method, then formed into pellets, and heated up to the decomposition temperature determined by the TG-DTA measurement. After heating, the fired substance cooled to room temperature was fractured in wet disruption, thereafter evaluating deposition of metal or metal oxide particles by XRD (X-ray diffraction structural analysis). Further, a state of a desired substance was determined according to presence or absence of structural change in the active substance.
  • XRD X-ray diffraction structural analysis
  • FIG. 2 is XRD measurement data of a sample obtained by mixing an active substance Li 1.33 Ti 1.66 O 4 and nickel acetate at 20:80 vol % and heat treating at 800° C. Signal peaks corresponding to nickel and the active substance Li 1.33 Ti 1.66 O 4 from the sample were detected, and deposition of metal particles was confirmed. It could be also confirmed that the structure of the active substance was not changed by the heat treatment.
  • FIG. 3 is XRD measurement data of a sample obtained by mixing an active substance Li 1.33 Ti 1.66 O 4 and nickel acetate at 20:80 vol % and heat treating at 800° C. Signal peaks corresponding to copper and the active substance Li 1.33 Ti 1.66 O 4 from the sample were detected, and deposition of metal particles was confirmed. It could be also confirmed that the structure of the active substance was not changed by the heat treatment.
  • a lithium ion secondary battery using a treated active substance and a lithium ion secondary battery using an untreated electrode material were prepared and battery characteristics (charge and discharge rate characteristics) were evaluated and compared. Firstly, a wet type battery was prepared and evaluated.
  • an active substance and a metal source compound were mixed.
  • the mixing ratio was set according to a ratio of a volume of a metal after deposition (normal temperature) and the volume of the active substance (normal temperature).
  • the obtained mixed powder was molded at an area pressure of 2 t/cm 2 by a tablet molding machine to obtain a molded article. Further, this molded article was thermally decomposed under predetermined conditions to thus obtain an electrode material made of the active substance on which a metal was deposited on the surface thereof.
  • Metal deposition was confirmed by XRD, and presence or absence of the structural change in the active substance before and after metal deposition were examined on the obtained electrode materials. Results as well as the details of the preparation conditions were shown in Table 1. It was confirmed from the results that a metal is deposited in any active substance in the examples by thermal decomposition of a metal source compound, and the active substance is not changed in the structure by the thermal decomposition treatment.
  • Examples 1A, 1B, and 2A shown in Table 1 correspond to methods for depositing a metal by thermal decomposition
  • Examples 2B, 3, 4, and 5 correspond to methods for depositing metals by vapor phase reduction.
  • a metal oxide is formed by thermal decomposition
  • a metal can be deposited from the metal oxide by carrying out vapor phase reduction after thermal decomposition.
  • Example 2 Example 2A Silver Spray dry 500° C. Li4Ti5O12 18.37 43.25 35.59 acetate + method Atmospheric Silver 38.10 44.29 77.40 paradigm air Paradigm 40.12 46.36 82.10 acetate
  • the above described active substance, Ketjen Black, and polyvinylidene fluoride were mixed in a weight ratio of 70:25:5, thereto was further added N-methyl pyrrolidone to form an active substance slip, and then, the active substance slip was uniformly coated on an aluminum foil using a doctor blade and dried.
  • a product obtained by punching out the active substance-coated aluminum sheet with a 14 mm ⁇ -punch (hereinafter, referred to as the “disc sheet electrode”) was vacuum-degassed and dried at 120° C. for 24 hours, and precisely weighed in a glove box at a dew point of ⁇ 65° C. or less.
  • An aluminum foil disc sheet obtained by punching out only an aluminum sheet with 14 mm ⁇ was also precisely weighed separately, and from the difference from the weighed value of the above described disc sheet electrode, the weight of the active substance applied on the disc sheet electrode was accurately calculated.
  • a wet type battery made of the thus obtain disc sheet electrode, lithium metal, a porous polypropylene separator, an electrolyte retaining sheet made from an unwoven fabric, and an organic electrolyte dissolved with a lithium ion (organic solvent having EC:DEC 1:1 vol dissolved with LiPF6 at 1 mol/L) was prepared.
  • a charge and discharge experiment was performed at charge and discharge rates of the prepared battery of 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C, and 5 C to measure a charge and discharge capacity per unit weight of the active substance.
  • a value used for comparison examination was calculated from a charge and discharge capacity in the fifth cycle in which battery characteristics are stabilized.
  • Similar batteries using an active substance without the treatment of the present invention were prepared and evaluated to be comparative examples. Results are shown in Table 2. It was confirmed from the results that any combination of an active substance and a metal source compound used in the experiment has higher discharge capacity as compared to batteries of comparative examples, and in particular, as a charge and discharge rate becomes higher, more excellent rapid charge and discharge characteristics can be obtained as compared to comparative examples.
  • an all solid-state battery using the metal-deposited active substance according to the present invention was prepared and the battery characteristics were evaluated.
  • the all solid-state battery was prepared by performing steps shown below in order:
  • a metal source compound and an active substance were weighed in a volume ratio defined above of 50:50 vol % and mixed, and the mixture was crushed and dispersed to obtain a mixed powder.
  • the obtained mixed powder was molded at an area pressure of 2 t/cm 2 by a tablet molding machine to obtain a molded article. Further, this molded article was thermally decomposed under predetermined conditions to thus obtain an electrode material made of the active substance on which a metal is deposited on the surface thereof.
  • Li 3.5 Si 0.5 P 0.5 O 4 powder with a median size of 0.54 ⁇ m was used for the solid electrolyte. 100 parts by weight of ethanol and 200 parts by weight of toluene were added to 100 parts by weight of this powder with a ball mill and wet mixed, and the mixture was then further charged with 16 parts by weight of a poly (vinyl butyral) binder and 4.8 parts by weight of benzylbutyl phthalate and mixed to prepare a solid electrolyte paste.
  • a collector paste was prepared by adding 15 parts by weight of ethyl cellulose as a binder and 65 parts by weight of dihydroterpineol as a solvent with respect to 100 parts by weight of powder obtained by mixing metal powder and active substance powder in an absolute specific gravity converted volume ratio of 80:20 vol, and the mixture was kneaded and dispersed with three rolls to prepare an electrode material paste.
  • the prepared solid electrolyte paste was formed into a sheet using a PET film as a substrate by the doctor blade method to obtain a lithium ion conductive inorganic substance sheet.
  • the electrode material paste and the collector paste were printed on the opposite side of the PET film of the obtained lithium ion conductive inorganic substance sheet by screen printing, heated at 80 to 100° C. for 5 to 10 minutes, and the paste was dried to obtain an active substance unit sheet on which the electrode material paste was printed on the lithium ion conductive inorganic substance sheet.
  • an active substance unit in which a storage and discharge electric potential of a lithium ion is noble is referred to as the “positive electrode unit”
  • an active substance unit in which a storage and discharge electric potential of a lithium ion is base is referred to as the “negative electrode unit”.
  • Such positive electrode unit and negative electrode unit were prepared and each PET film was peeled off, thereafter laminating alternately so as to be interposed with a lithium ion conductive inorganic substance.
  • the positive electrode collector was only extended in one end surface
  • the negative electrode collector was only extended in the other surface so that the positive electrode unit and the negative electrode unit were shifted and laminated.
  • the laminated article was further sandwiched with a protective layer obtained by overlapping 50 layers of only lithium ion conductive inorganic sheets and molded at a temperature of 80° C. at a pressure of 1000 kgf/cm 2 , and then cut to prepare a laminated block.
  • the temperature of the obtained laminated block was increased up to 800° C. at a temperature increasing rate of 200° C./hour in the atmosphere, and the laminated block was fired while maintaining the temperature for 8 hours.
  • the laminated block was naturally cooled after firing.
  • a width of each lithium ion conductive organic substance in the thus obtained laminated article after firing was 7 ⁇ m
  • the width of the positive electrode unit was 5 ⁇ m
  • the width of the negative electrode unit was 6 ⁇ m.
  • the length, width and height of the laminated block were 3 mm ⁇ 2.1 mm ⁇ 0.1 mm, respectively.
  • An extracting electrode paste was applied on an end surface of the laminated article, and thermally cured at 150° C. for 30 minutes. Further, one pair of extracting electrodes was formed to obtain an all solid-state lithium ion secondary battery.
  • a thermally curable conductive paste made of silver powder, an epoxy resin, a solvent, and a curing agent was used.
  • a charge and discharge experiment was performed at charge and discharge rates of the prepared battery of 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C, and 5 C to measure a charge and discharge capacity per unit weight of the active substance.
  • a value used for comparison examination was calculated from a charge and discharge capacity in the fifth cycle in which battery characteristics are stabilized. Note that similar batteries using active substances without the treatment of the present invention were prepared and evaluated to be comparative examples. Results are shown in Table 3.
  • Example 1A in Table 1 were used for preparation of the positive electrode unit, and the conditions of Example 2B in Table 1 were used for preparation of the negative electrode unit.
  • the present invention relates to an electrode material and a battery produced using the electrode material, and a battery having small internal resistance and excellent charge and discharge rate characteristics can be produced. Since high energy efficiency can be obtained and a waste heat amount is less to reduce environmental burdens, in particular, such a battery is effective as a power tool that requires instantaneously large output and has high applicability as a secondary battery for an electric automobile such as, for example, a hybrid car.

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